Polyfluorocycloalkyl phosphates

ABSTRACT

Polyfluorocycloalkyl phosphate compounds, the method of preparing these polyfluorocycloalkyl phosphate compounds, and the use of these polyfluorocycloalkyl phosphate compounds as grease and oil resistant sizes are disclosed.

uluwu DlitllCD J Moyer POLYFLUOROCYCLOALKYL PHOSPHATES Inventor: Ronald C. Moyer, North Kingstown,

Assignee: Air Products and Chemicals, Inc.,

Allentown, Pa.

Filed: Mar. 22, 1972 Appl. No.: 236,978

Related U.S. Application Data Continuation-impart of Ser. No. 39,175, May 20,

1970, abandoned, which is a continuation-in-part of Ser. No. 844,l97, July 23, 1969, abandoned.

us. Cl. 260/924, 106/15 FP, 117/152,

260/239 BC, 260/247, 260/293.5l, 260/309, 260/925, 260/933, 260/955, 260/974, 260/980 UNITED STATES PATENTS 3,254,]05 5/l966 Rosen 260/955 X Primary Examiner--Ant0n H. Sutto Attorney, Agent, or Firm-Barry Moyerman [57] ABSTRACT Polyfluorocycloalkyl phosphate compounds, the method of preparing these polyfluorocycloalkyl phosphate compounds, and the use of these polyfluorocycloalkyl phosphate compounds as grease and oil resistant sizes are disclosed.

23 Claims, No Drawings CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of application Ser. No. 39,175 filed May 20, I970 now abandoned, which in turn is a continuation-in-part of parent application Ser. No. 844,197 filed July 23, 1969, now abandoned.

BACKGROUND OF THE INVENTION The present invention relates to a novel class of fluoroalkyl compounds and more particularly, to polyfluorocycloalkyl phosphate compounds which can be used to render textiles, paper and other similar materials grease and oil resistant.

Certain polyfluoroalkyl phosphates are known in the art and are defined by the general formula where m is'an integer from 4 to 12, n is an integer from l to 16, y is a number of average value from 1.0 to 2.5 and M stands for water-solubilizing cation such as hydrogen, an alkali-metal, ammonium or substituted ammonium. Certain of these polyfluoroalkyl phosphates, whose alkyl structure contains a straight chain of at least 8 carbon atoms and not less than 9 fluorine atoms, can be used to render paper oil repellent.

SUMMARY OF THE INVENTION An object of the present invention is to provide novel polyfluorocycloalkyl phosphate compounds which are useful in imparting grease and oil repellency to textile materials, paper and similar materials.

Another object of the present invention is to provide a method for preparing polyfluorocycloalkyl phosphates.

Still another object of the present invention is to provide a method of treating textile materials, paper and similar materials with polyfluorocycloalkyl phosphate compounds to render said materials grease and oil repellent.

These and other objects of the present invention are accomplished using a polyfluorocyclohexanealkyl phosphate compound or the phosphochloridate intermediate of such compounds which have the formula where n is an integer of from I to 4 and K; is fluorine or a C to C perfluoroalkyl group substituted on the 2, 3 or 4 position of cyclohexane ring. In particular, the novel polyfluorocyclohexanealkyl phosphate compounds of the present invention are those represented by formulas (III) and (IV):

where K; is fluorine or a C 1 to C perfluoroalkyl group substituted on the 2, 3 or 4 position of the cyclohexane ring, n is an integer of from I to 4, a is an integer of from 1 to 2 and X in each occurance is independently selected from chlorine or any member of OM where M is a water-solubilizing cation of the group consisting of hydrogen, alkali metal (sodium or potassium), ammonium or substituted ammonium.

The values of K,, n and X for the pyrophosphates of formula IV are the same as formula III. Although a and m of IV may be integers of one or more in most instances, their values will only be one.

From the above structural formulas it can be seen that certain compounds will have only a single X, in which case it may have a value of chlorine or an OM radical where M is hydrogen, alkali metal, ammonium or substituted ammonium derived from a primary, secondary or tertiary amine. However, pyroesters IV and bisesters III have at least two Xs present. In this instance, each X may then be independently selected from chlorine or OM and any of the values for M. This naturally includes individual compounds where each of the Xs have radicals which are the same as well as compounds having a plurality of Xs where each is different from the other.

The following table illustrates but a few of the polyfluorocyclohexanealkyl phosphates falling within the purview of the foregoing structural formulas:

Ring Rosition of K,

'n'n 1 'n 'np-n-n-n-n n-n J" Jib A 41 awea aabrsazse-ewuJs-zs It has been discovered that these compounds have very useful properties, including the property of rendering textile materials, paper and similar materials resistant to penetration by grease and oil when applied to such materials at a concentration within the range as low as 0.1 to 2.0 percent on weight of substrate.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel phosphate compounds of this invention may be prepared by two different routes having per-' ence of an organic liquid diluent such as benzene, toluene, or xylene. The product produced in accordance with such method provides a complex mixture of perfluorocycloalkyl phosphate compounds, said mixture containing a major amount of compounds having structures Ill and 1V.

In the above reaction, certain perfluorocyclohexane alkanols are reacted with the preferred reactant, phosphorus pentoxide, in the ratio of (alkanol: phosphorus pentoxide) from about 1:1 to about 4:1 and preferably from about 1.511 to about 3:1. It has been found that the reaction may be conducted at temperatures of from about 30C to about 200C and preferably from about 45C to about 130C. Below temperatures of about 30C, it has been found that the reaction takes too long to be practical. Above about 200C, the product produced by the reaction will not provide desirable results such as oil holdout when applied to paper.

in accordance with the second route, a perfluorocyclohexane alkanol of the formula l(/(I F C,,H ,,OH, where K, is fluorine or a perfluoroalkyl group of from 1 to 4 carbon atoms and where n is an integer from 1 to 4, is reacted with a phosphorus oxyhalide composition such as phosphorus oxychloride (POCI in the presence of an acid acceptor such as pyridine, and in the optional presence of an organic liquid diluent such as benzene. One to two moles of the perfluorocyclohexane alkanol are employed per mole of phosphorus oxychloride and the reaction is preferably effected by heating the mixture at reflux temperature to obtain an intermediate phosphochloridate reaction product. The product prepared in accordance with the phosphorus oxychloride route yields a composition containing major amounts of compounds corresponding to formula ill and no pyrophosphates of IV.

in lieu of phosphorus oxychloride in the synthesis of the novel phosphate compounds of the invention, phos phorus oxybromide or phosphorus oxyiodide may also be used. When phosphorus oxyhalides are used, the intermediate reaction product is hydrolyzed to form the required phosphate ester, and any tertiary amine that accepts no other functional groups may be used as an acid acceptor. Examples of such acid acceptors are pyridine, trimethylamine, triethylamine, tripropylamine, N. N-dimethylaniline, N, N-diethylaniline and the like. Suitable solvents or media for the reaction are non-proton donating solvents, such as aromatic and aliphatic hydrocarbons, halohydrocarbons, ethers and the like. Specific examples of solvents which may be used include benzene, toluene, chlorobenzene, hexane, octane, mixed alkanes, lchlorobutane, carbon tetrachloride, dipropyl ether, dibutyl ether and dioxane. The reaction may be conducted at temperatures between 0C and 110C, and preferably at a temperature between 50C and 100C for the first stage of the reaction.

The resulting products of the two above-described synthesis routes may be isolated as free acids and then converted, by pH adjustment with an appropriate base, into alkali-metal (sodium or potassium), ammonium or substituted ammonium salts. The substituted ammonium salts may be prepared from commonly available, water soluble primary, secondary or tertiary amines which are inclusive only by way of example of organic amines, such as alkyl amines, alkanolamines, nitrogen containing hetcrocyclics, cyclic amines, polyamines, and the like. Alkyl amines may be primary, secondary or tertiary and may have alkyl groups having 1 to 6 carbon atoms. The alkyls may be straight chain or branch ed like methylamine, ethylamine, diethylamine, triethylamine, tripropylamine, diisobutylamine. Alkyl amines also encompass mixed amines such as N-ethyl dipropylamine, N-ethyl-N-methyl propylamine, N, N- dimethyl butylamine, etc. Alkanolamines which form substituted ammonium salts with the taught compounds usually have from 1 to 3 hydroxyl groups and may also be primary, secondary, or tertiary amines. Examples of suitable alkanolamines are monoethanolamine, diethanolamine, triethanolamine, bis (2- hydroxy-propyl) amine and pentanolamine and related compounds having 2 and 3 hydroxy groups and in the range of from 2 to 10 carbon atoms. Substituted ammonium salts may be prepared from nitrogen containing heterocycles including aromatic and non-aromatic types which may or may not be substituted, like imidazole, morpholine, piperidine and alkyl substituted heterocyclics having 1 to 6 carbon atoms like 2-ethyl imidazole. Cyclic amines and especially bicyclic compounds like triethylenediamine are useful salt forming agents. Suitable polyamines are ethylenediamine, l, 2 propanediamine, diethylene triamine, etc.

In preparing water soluble salts of formulas Ill and IV the foregoing compounds are ordinarily incorporated into the reaction mixture containing the mono, his and pyroester compounds. The quantity of salt forming compound used in the reaction mixture is based upon that amount which would be consistant with customary practices in connection with the particular substrate to which the composition is to be applied. For applications to paper materials salt forming compounds e.g...- .diethanolamines are used in an amount sufficient to provide the mixture with a pH in a range from about 2 or 3 to about 7, however, an amount to a pH of about 5 is regarded as most preferred. Then too, some stocks have a tendency to degrade when the pH is very low, in which case an amount of salt forming compound is used to provide the compositions with a pH as high as l 2 (\ccordingly, the pH may be adjustedgenerally to a range of from about 2 to about 12 and more preferable from about 4 to about 10 for most applications to paper, textiles and other related substrates.

Thus, oil and grease resistant polyfluorocycloalkyl phosphates compositions typically may contain only by way of illustration one or more of the following: monoundecafluorocyclohexanemethyl phosphate (monoester), bis-undecafluorocyclohexanemethyl phosphate Monoester Pyroester Other polyphosphate esters may also be present, but at lower concentrations 3 percent) for products prepared with a molar ratio of 3 moles of perfluorocyclohexane alkanol to each mole of phosphorus pentoxide.

As mentioned above, preparation of the polyfluorocycloalkyl phosphates disclosed herein results in mixtures containing various mono, his and pyrophosphate esters. These reaction mixtures as well as their individual phosphorus containing compounds can be effectively employed on substrates to impart oil and grease resistant properties thereto. Accordingly, the various novel esters of the reaction mixture can be isolated by standard extraction processes using solvents, acids and bases. Typically, both his and pyrophosphate esters are ether extractable from. aqueous basic solutions, such as from solutions of standardized alkali metal hydroxides like sodium and potassium hydroxides. Monoester is not extracted by the ether and remains in the aqueous layer. However, all the phosphate esters, mono, bis and pyro, are ether extractable from aqueous acid solutions, such as those acidified by hydrochloric acid. In this instance, aqueous acidether extraction leaves diethanolamine in the aqueous layer free of phosphate esters.

The invention will be illustrated by the following specific examples, it being understood that there is no intention to be necessarily limited by any details thereof since variations can be made within the scope of the invention. Parts mentioned in these examples are by weight.

EXAMPLE I Mono 1, l-dihydroperfluorocyclohexanemethylphosphate was prepared by reacting 31.0 grams (0.1 moles) of 1, l-dihydroperfluorocyclohexane methanol with 15.4 grams (0.1 moles) of phosphorus oxychloride. The ingredients were heated to 100C and a few drops of pyridine were added. Gaseous hydrochloric acid evolved moderately from the reaction for 7 hours. After this time the reaction mixture contained three components: POCI (C F CH O) P(O)CL and (C F CH O)P(O)Cl as evidenced by vapor phase chromatography. No fluoroalkanol remained.

Distillation at atmospheric pressure was employed to remove remaining POCl Distillation, at -20 mm pressure, was then employed to obtain the desired product (C 1 CH O)P(O)C1 which was collected over a temperature range of 94-140C. The higher boiling impurity (C F CH O) P(O)CI remained behind as a distillation residue. The distilled product (C F CH O)P(O)CI was obtained and identified by elemental analysis.

Mono 1 ,1 -dihydroperfluorocyclohexanemethylphosphate was obtained by the following reaction:

and identified by titration with 0.1 N NaOH solution in ethanol. EXAMPLE ll Bis-l l ,1-dihydroperfluorocyclohexanemethyl] phosphate was prepared by reacting 62.4 grams (0.2 moles) of perfluorocyclohexane methanol with 15.5 grams (0.1 moles) of phosphorus oxychloride. The reaction mixture was heated to C and a few drops of pyridine were added. Gaseous hydrochloric acid evolved moderately from the reaction for 6 hours.

Removal by distillation of the more volatile components POCl and (C F CH O)P(O)Cl provided product (C F ,CH O) P(O)Cl as an amber colored distillation residue in 86% yield (60.8 grams). Micro elemental analyses were in reasonably good agreement with the expected values.

Hydrolysis of (C F, CH O) P(O)Cl to (C F CH O) P(O)OH was accomplished by mixing the stoichiometric quantity of water with (C F,,CH O) P(O)Cl and stirring at room temperature overnight. The solid acid (C F CH O) P(O)OH was identified by titration with 0.1 N NaOl-l solutions in ethanol.

EXAMPLE 111 A mixture of mono-1 ,l-dihydroperfluorocyclohexanemethyl-phosphate, bis-[ 1,1-dihydroperfluorocyclohexanemethyl] phosphate, and bis-[ l l -dihydroperfluorocyclohexanemethyl] pyrophosphate was obtained by adding 868.0'grams (2.8 moles) of 1,1-dihydroperfluorocyclohexane methanol and 131.6 grams (0.91 moles) of phosphorus pentoxide to a flame dried, nitrogen purged flask. The heterogeneous mixture was heated to F and stirred vigorously for 5 hours. After this time solution had occurred. A vacuum of 2 inches Hg and a temperature of F was applied to the heated flask to remove dioxane and unreacted alcohol. The desired mixture of 1 ,1 dihydroperfluorocyclohexanemethylphosphates was poured from the reaction flask and allowed to crystallize. A greater than 99 percent yield of the phosphate compositions was obtained by this reaction. EXAMPLE 11V The method of Example 111 was employed for reacting 18.1 parts l,1-dihydro-(tridecafluoro-4-methyl cyclohexane) methanol with 2.4 parts of phosphorus pentoxide (molar ratio 3:1 The heterogeneous mixture was stirred for 6 hours at a temperature not exceeding 55C. A mixture of mono, bis and pyro (tridecafluoro [4-methyl] cyclohexane) methylphosphates were collected in 96 percent yield. The product of Example IV was evaluated as an oleophobic paper size, in accordance with the procedure set forth in Example X.

EXAMPLE V (Nonadecafluoro-4-n-butylcyclohexane) methanol (25.6 parts) was reacted with phosphorus pentoxide (2.4 parts) by the procedure described in Example 111. The mixture of mono, his and pyro (nonadecafluoro-4- n-butylcyclohexane) methylphosphates thus formed, was collected in 95 percent yield. EXAMPLE V1 The application of polyfluorocycloalkyl phosphate compounds to such materials as paper and textile materials is most readily done in industry from aqueous solutions. For example, aqueous solutions of the 1,1- dihydroperfluorocyclohexanemethylphosphates are easily made by first neutralizing an isopropanol solution of mono-l ,l-dihydroperfluorocyclohexanemethylphosphate, bis-( l l -dihydroperfluorocyclohexanemethyl) phosphate, bis-(l,l-dihydroperfluorocyclohexanemethyl) pyrophosphate or a mixture of Extraction of this solution with ether results in the isolation of his (B) and monoesters (C). The latter monoesters are formed by hydrolysis of the pyrophosphates which were present. The mixture of bis and monoesters (derived from the pyrophosphates) are titrated potentionmetrically with standardized base resulting in two plateaus in the plot of pH vs. moles of base added. The first plateau minus the second plateau gives the percent bisester while the second plateau gives the percent pyrophosphate ester. Procedure 11 An alternative method of analysis can be employed using nuclear magnetic resonance such as by a phosphorus NMR instrument. The products show absorption peaks at specified positions relative to the reference material phosphorus trioxide (P 0 These peaks are:

Mono ester +1140 ppm Bis ester +1 16.1 ppm Pyro ester +126.5 ppm 1n the case of Example V11 determination of the mono, his and pyrophosphate esters indicated the following values for the components. The weight percent is based on the total weight of ether extractables i.e....- weight of A, B and C in Procedure 1.

mono-. his and pyro-(1,1-dihydroperfluorocyclohexanemethyl) phosphate with diethanolamine to a pH sufficient to render the polyfluorocycloalkylphosphates soluble and diluting to a desired concentration using isopropanol or water. EXAMPLE V11 Using the product mixture of Example 111, a water soluble formulation was prepared by mixing 28 parts of said product mixture, 6 parts of diethanolamine, 33 parts of isopropanol and 33 parts of water. This formulation provides a phosphate solution containing 33 percent solids.

ln determining the amounts of mono, bis and pyrophosphate esters in the reaction product the following procedures may be used. Procedure 1 A measured volume of the solution of diethanolamine salts of the phosphate esters is taken up in ether and then treated with water and a measured volume of standardized 0.5 N sodium hydroxide. The ether layer contains the his and pyrophosphate esters. The monophosphate ester is extracted with the aqueous standardized alkali. The alkaline extract is acidified with an acid, such as concentrated HCl and extraction with ether results in the monoester (A) which can be titrated potentiometrically with a standardized base. From the first or second plateau of this titration in the plot of pH vs. moles of base added, the percent monoester can be determined.

The ether extract containing the bis and pyrophosphate esters are acidified with a dilute HCl solution.

EXAMPLE V111 The ammonium salt of the product mixture of Exam ple 111 was obtained by mixing 35.4 grams of said product mixture, 6.1 grams of aqueous ammonia (28 percent), 37.1 grams of isopropyl alcohol and 32.7 grams of water.

To demonstrate the utility of the water soluble formulations of the present invention as oleophobic paper sizing agents, the formulations were applied to two types of paper: (a) a 50 lb. Natural Kraft (softwood), 0.6 percent rosin/alum sized with a basis weight of 50 pounds per 3,000 square feet, and (b) Consolith paper, a bleached coating base stock with a furnish composed of ground wood, sulfite and Kraft pulps, with a basis weight of 26 pounds per 3,000 square feet and containing 0.25 percent rosin/alum size. The application of said water soluble formulations to these papers was accomplished in each instance by the following technique:

l. The paper which was coated was anchored to an 8 /2 inch X l 1 inch wooden frame on all four sides with masking tape.

2. The frame was placed over a glass plate nearly the same size to insure a solid paper surface during drawdown.

3. A 20 gram aqueous sample of the desired concentration was made up by dilution of the 33 percent stock solution. (Example V11) 4. A glass plate was butted against the head of the framed paper with a sheet of polyethylene spanning the gap between the glass plate and the paper frame.

5. The sample solution was poured on the glass plate.

6. A No. 18 wire wound rod was used to draw the sample solution down over mounted paper.

7. Excess solution was wiped from masking tape and the frame was placed into an l lC oven less than 15 seconds after drawdown.

8. The paper was oven dried approximately minutes.

9. Testing was done after removal from the oven, according to the lmproved Test for Grease Penetration; Paper, Film and Foil Converter, March, 1964, which test is specifically incorporated by reference herein.

in accordance with the aforementioned test, an accelerated comparison of the relative rates at which oils or greases, such as commonly found in foodstuffs, may be expected to penetrate papers such as uncoated or unimpregnated grease-proof, glassine and vegetable parchment. The apparatus which is used includes;

. EXAMPLE 1x Using the aforementioned procedures, the mixture of Example lll was applied to a 50 pound per ream natural Kraft Softwood paper 0.6 percent rosin/alum sized. The drying was accomplished at l 10C for about 3 minutes. Table A compares the concentration of applied fluorochemical solids with the number of hours resistance to grease penetration by three oil or grease materials, viz., nujol, corn and lard using the water soluble formulation of Example Vll. Table B makes a similar comparison using the ammonium salt of the mixture of Example ill, in which the ammonium salt was prepared in a manner similar to the procedure of Example Vlll. All tests were terminated after 72 hours and marked fl g l ln thgfollowing tables the concentration percent on weight of paper is abbreviated as Conc. %O.W.P., and the term immediately" is abbreviated. as. lmm .-f

TABLE A Grease Holdout (Hours) Paper Uncreased Conc. %O.W.P. 2.0 1.7 1.5 1.4 1.25 1.0 0.5

Nujol 72+ 72+ 72+ 6.5 3.5 0.25 lmmed. Corn 72+ 72+ 72+ 26.75 9 1.25 lmmed. Lard 72+ 72+ 72+ 20.5 0.25 lmmed.

Paper Creased Away Conc. %-o.w.1 2.0 1.7 1.5 1.4 1.25 1.0 0.5 Nujol 72+ 72+ 72+ 72+ 72+ lmmed. lmmed. Corn 72+ 72+ 72+ 50 47 lmmed. lmmed. Lard 72+ 72+ 72+ 6 0.25 0.5 lmmed.

Paper Creased Into Conc. o.w.1=. 2.0 1.7 1.5 1.4 1.25 1.0 0.5 NUJOI 72+ 72+ 72+ 72+ 72+ lmmed. lmmed. Corn 72+ 72+ 72+ 50 0.25 0.25 lmmed. Lard 72+ 72+ 72+ 0.5 0.25 lmmed. lmmed.

l. A tube of any rigid material, 2.5 cm (1 in.) ID and TABLE B at least 2.5 cm (1 in.) in height, the ends of which have been smoothed. Grease Holdout (Hours) 2. A pipet or medicine dropper, calibrated to deliver Paper [Increased 1.1 ml. Conc. a-owP. 2.0 0.5 3. Round-grained sand, Ottawa cement testing sand N l l 72+ 72 l d screened to pass a No. 20 and be retained on a No. 72+ 2%, 3 sieve. Lard 72+ 3.25 lmmed. 4. Sheets of whitezcoated and calendered 80 lb. book Paper Creased Away paper, 104 g/m 70 lb. at least the same size as the Conc. %-O.W.P. 2.0 1.0 0.5

Nujol 2.5 0.25 lmmed. test specimen, preferably much larger. Com 20 lmmfli mm 5. A stopwatch or laboratory timer. Lard 9 0.25 lmmed. The reagents, peanut oil, l'lUjOl, liquid lard, and corn oil 1 Paper Creased lnto are separately placed in bottles 1 10 ml In each bottle) Com o w p Z0 1.0 5 with 1.0 gram of an oil soluble red dye. g jol 3.75 :mmeg. }mmeg. Each specimen is then placed on a sheet of the book 3,; 9 'T 2$;

paper resting on a smooth fiat surface. An end of the tube placed on the specimen and 5 grams of sand are placed in the tube. The purpose of the tube is solely to ensure a uniform area of the sand pile. Using the pipet or medicine dropper, 1.1 ml of the colored oil or grease is added to the sand, the tube is removed, and the timing device is started. Three conditions of folds exist for the specimen, namely:

A. No Fold B. Creased into C. Creased Away The test proceeds for 72 hours at 60C or until the stain strikes through the treated paper and stains the book paper beneath it.

Equivalent, but not necessarily identical, results are obtained using the polyfluorocycloalkyl phosphate compound having the formula (C F C H O)PO(Na) tween Whatman No. I paper and pressed under a 26 TABLE D pound load (4.5 square inch base) for 30 seconds. Wet pickups on the weight of the paper average 110 per- Bis- Mnnn. cent Sample l/P,O, Pyrophosphutc phosphate phosphate The specimens were dried for 1 hour at 60C in a 5 A 3/1 2 7 42 6 26.77 forced draft oven. They were then removed and stored B 28/1 0340 45-53 flat, under a 1 pound load at approximately 23 C at 50 D 20/ (L35 3258 4633 percent relative humidity until ready for testing. E l4-50 24-52 41358 Half of the specimens were creased twice, top and bottom sides at right angles and through the center of 10 The lower ratio samples, in particular D and E, apthe sheet. Otherwise, the test was performed as outparently contain a considerable amount of polyphoslined in Improved Test for Grease Penetration", Paphates with three or more phosphate linkages since the per, Film and Foil Converter, March, 1964. Table C total pyrophosphate, monophosphate and biscompares the concentration of applied fluorochemical phosphate adds up to a figure considerably less than solids with the number of hours resistance to grease 100 percent. penetration by four oil and grease materials, viz, nujol, EXAMPLE XIII corn, lard and peanut oil. This table shows that grease A comparison was made of the oleophobicity of holdout of greater than 72 hours can be obtained using products of sample A and E in Example XII. Tests were the formulations ofthe present invention. All tests were conducted on bleached Kraft waterleaf paper. The terminated after 72 hou rs andnlarltgij lflp thi SLQ- paper contained no rosin/alum size and had a basis ble, the concentration percent on weight of paper is ab weight of 41 lbs/3,000 ft The results are given in the breviated Cone. %O.W.P.". [following table.

TABLE C Grease Holdout (Hours) Paper Uncreased Conc. %-O.W.P. 1.3 .1 0.9 0.7 0.5 0.3 0.1

Nujol 72+ 72+ 72+ 72+ 60.4 0.5 0.1 Corn 72+ 72+ 72+ 72+ 72+ 60.2 0.07 Lard 72+ 72+ 72+ 72+ 72+ 39.3 0.08 Peanut 72+ 72+ 72+ 72+ 72+ 40.3 0.07

Paper Creased Cone. %-o.w.P. 1.3 1.1 0.9 0.7 0.5 0.3 0.1 Nujol 72+ 72+ 72+ 54.1 1.7 0.1 0.1 Corn 72+ 72+ 72+ 72+ 72+ 1.6 0.07 Lard 72+ 72+ 72+ 72+ 19.9 0.5 0.03 Peanut 72+ 72+ 72+ 72+ 25.7 0.2 0.03

Equivalent, but not necessarily identical, results are TABLE E obtained using the polyfluorocycloalkyl phosphate compound having the formula (C F ,C H O) Fluorochcmical Fun Peanut on PO(ONH4) 45 Sample on Wt. of Paper Holdout at C (Hours) EXAMPLE XI A 0.36 391 Cotton IS chemically modified by reaction with A (C F CI-I O) P(O)(OH) and then cured in the presence 33;

of urea at a temperature between I40 to 160C for I hour. A chemical bonding of the perfluorocyclohexyl phosphate to the cellulose hydroxyl of the cotton occurs.

A similar bonding is obtained when the phosphochloridates (C F CH O) P(O)CI and (C F CH O)P(O)CI are reacted with cotton and urea to form cellulose phosphates.

EXAMPLE XII Mixtures of the mono-, bis-, and pyrophosphates of l,I-dihydroperfluorocyclohexane methanol (I) were obtained by reacting compound I with phosphorus pentoxide in varying ratios. The procedure for their preparation corresponds to that described in Example III, but the reaction mixture was stirred at llO-I20C for 5 hours. Analyses by Procedure I of Example VII of the products prepared with these varying ratios are shown in the following table.

Test showed evidence of crawling (horizontal wicking of the test oil on the paper surface).

While the product of sample E had less pyrophosphate than the product of sample A (see Example XII), sample E still provides good oleophobicity. The presence of pyrophosphates and possibly polyphosphates of an undetermined nature apparently contribute to the oleophobicity of the product.

EXAMPLE XIV A portion of a product corresponding to that prepared in Example VII was hydrolyzed using Procedure I and the total of the original monoester (A), bisester(B), and monoester formed by hydrolysis of pyrophosphate (C) was reformulated into an aqueous solu tion by mixing 28 parts of the mixture of (A), (B) and (C), 6 parts of diethanolamine, 33 parts of isopropanol and 33 parts of water. This reformulated solution when composition.

analyzed for pyrophosphate by Procedure I gave a value which is regarded as being between and 3 percent. This value is within the experimental error of the analysis (i 3 percent).

The original product of Example Vll had pyrophosphate content of about percent.

Acomparison was made of the oleophobic properties of the reformulated hydrolyzed product and the original product prepared in Example VII. These results are shown below.

TABLE F Creased Peanut Oil Holdout" Fluorochemical O.W.P.

at 60C (Hours) Sample Max. Min. Average 03% Pyrophosphate 1.26 8 24 1.0 7.5 .94 2.0 .5 .9 20% Pyrophosphate 1.27 72+ 72+ 72+ Tl ie paper used was bleached sulphite paper of the type described in Example VII. The results indicate more prominent oleophobic properties when pyrophosphate esters are included in the EXAMPLE XV The desirability of having pyrophosphates present in formulations is further illustrated by the results of the following application tests. These tests were conducted with a 41 lb/ream bleached Kraft waterleaf. This paper contained no rosin/alum size. The results are shown below.

TABLE G Flat Peanut 7; Fluorochemical Oil Holdout Sample O.W.P. at 60C (Hours) 0-37c Pyrophosphates" 0.44 2l6 .29 SI 20% pyrophosphates .36 39l .20 52 (Crawling) Preparation referred to in Example XIV.

Samples A to E were screened further for performance using the test for creased peanut oil holdout described in Example Vlll.

Creased Peanut Oil Holdoufi- Fluorochemical at 60C (Hours) Sample O.W,P. Min. Average Bleached sulfite papers of the type described in Example VII were used in these tests. The maximum and minimum vulucs are the results of [0 replicates.

-sion may be imparted to materials treated with the novel polyfluorocycloalkylphosphate compounds of this invention. Said compounds also have the required water solubility to be useful as surface active agents and are well adapted to be used as dispersing agents in Where the novel compounds of this invention are used for oil repellency purposes, said compounds may be applied to a great variety of semiporous substrates, such as textile fabric, textile yarn, leather, paper, plastic sheeting, wood, ceramic clays as well as manufactured articles made therefrom, such as wearing apparel, wall paper, paper bags, cardboard boxes, porous earthenware, etc.

The treatment of textile fibers or other waterinsoluble solid materials with the novel polyfluorocycloalkylphosphates of this invention may be achieved by padding, spraying or brushing, using aqueous solutions of said phosphates. Alternatively, the waterinsoluble solid materials may be treated with retention aids, water-soluble polymer possessing cationic nitrogen atoms, which cause the polyfluorocycloalkylphosphates to exhaust into the water-insoluble solid material from an aqueous solution. The polyfluorocycloalkylphosphates can also be employed as internal sizing during the formation of paper.

Obviously, many modifications and variations of the invention as hereinbefore set forth can be made without departing from the spirit and scope thereof and, therefore, only such limitations should be imposed as are indicated in the appended claims.

I Claim:

1. A perfluorocyclohexyl phosphate selected from compounds of the formula:

" selected from chlorine or any member of OM where M is a water-solubilizing cation of the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium.

2. The phosphate compound of claim 1 wherein the eam emales @fleli p a h ixh- 3. The phosphate compound of claim 2 wherein X is OM, M is hydrogen, a is l, n is 2 and K, is F.

4. The phosphate compound of claim 2 wherein X is OM, M is hydrogen, a is l, n is l and K, is F.

5. The phosphate compound of claim 2 wherein X is Cl, a is l, n is l and K is F.

6. The phosphate compound of claim 2 wherein X is Cl, a is 2, n is l and K is F.

7. The phosphate compound of claim 2 wherein each X is OM, M is diethanol ammonium, a is l, n is 1 and K, is F.

ii. The phosphate compound of claim 2 wherein X is OM, M is diethanol ammonium, a is 2, n is l and K, is F.

9. The phosphate compound of claim 1 wherein the structural formula is 10. The phosphate compound of claim 9 wherein X is OM, M is hydrogen, n is l and K is F.

11. The phosphate compound of claim 9 wherein X is OM, M is diethanol ammonium, n is l and K; is F.

12. A perfluorocyclohexyl phosphate composition comprising mixtures of mono, bis and pyro compounds of the formulas:

wherein K is fluorine or a C to C perfluoroalkyl group substituted on the 2, 3 or 4 position of the cyclohexane ring, n is an integer of from l to 4, a is an integer of from l to 2 and X in each occurance is independently selected from chlorine or any member of OM where M is a water-solubilizing cation of the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium.

13. The composition of claim 12 wherein the mixture comprises compounds in which X is OM, M is hydrogen, a is l, n is 2 and K, is F.

14. The composition of claim 12 wherein the mixture comprises compounds in which X is OM, M is hydrogen,aisl,nislandl(,isF.

15. The composition of claim 12 wherein the mixture comprises compounds in which X is Cl, a is l, n is l and K, is F.

16. The composition of claim 12 wherein the mixture comprises compounds in which X is Cl, a is 2, n is l and K, is F.

17. The composition of claim 1'12 wherein the mixture comprises compounds in which X is OM, M is diethanol ammonium, a is 2, n is 4 and X, is F.

18. The composition of claim 12 wherein the mixture comprises compounds in which X is OM, M is diethanol ammonium, a is l, n is l and K, is F.

19. The composition of claim 12 wherein the mixture comprises compounds in which X is OM, M is diethanol ammonium, a is l and 2, n is 1 and K, is F.

20. The composition ofclaim 12 including a mixture of 21. The composition of claim 20 wherein K, is F, n is l and X is Cl.

22. The composition of claim 20 wherein X, is F, X is OM, M is ammonium or substituted ammonium and n is l.

23. The composition of claim 20 wherein M is F, X

is OM, M is a diethanol ammonium and n is 1.

a}: a: a: :l: :l: 

2. The phosphate compound of claim 1 wherein the structural formula is (KfC6F10CnH2nO)aPO(X)3 a.
 3. The phosphate compound of claim 2 wherein X is OM, M is hydrogen, a is 1, n is 2 and Kf is F.
 4. The phosphate compound of claim 2 wherein X is OM, M is hydrogen, a is 1, n is 1 and Kf is F.
 5. The phosphate compound of claim 2 wherein X is Cl, a is 1, n is 1 and Kf is F.
 6. The phosphate compound of claim 2 wherein X is Cl, a is 2, n is 1 and Kf is F.
 7. The phosphate compound of claim 2 wherein each X is OM, M is diethanol ammonium, a is 1, n is 1 and Kf is F.
 8. The phosphate compound of claim 2 wherein X is OM, M is diethanol ammonium, a is 2, n is 1 and Kf is F.
 9. The phosphate compound of claim 1 wherein the structural formula is
 10. The phosphate compound of claim 9 wherein X is OM, M is hydrogen, n is 1 and Kf is F.
 11. The phosphate compound of claim 9 wherein X is OM, M is diethanol ammonium, n is 1 and Kf is F.
 12. A perfluorocyclohexyl phosphate composition comprising mixtures of mono, bis and pyro compounds of the formulas: (KfC6F10CnH2nO)aPO(X)3 a and
 13. The composition of claim 12 wherein the mixture comprises compounds in which X is OM, M is hydrogen, a is 1, n is 2 and Kf is F.
 14. The composition of claim 12 wherein the mixture comprises compounds in which X is OM, M is hydrogen, a is 1, n is 1 and Kf is F.
 15. The composition of claim 12 wherein the mixture comprises compounds in which X is Cl, a is 1, n is 1 and Kf is F.
 16. The composition of claim 12 wherein the mixture comprises compounds in which X is Cl, a is 2, n is 1 and Kf is F.
 17. The composition of claim 12 wherein the mixture comprises compounds in which X is OM, M is diethanol ammonium, a is 2, n is 4 and Kf is F.
 18. The composition of claim 12 wherein the mixture comprises compounds in which X is OM, M is diethanol ammonium, a is 1, n is 1 and Kf is F.
 19. The composition of claim 12 wherein the mixture comprises compounds in which X is OM, M is diethanol ammonium, a is 1 and 2, n is 1 and Kf is F.
 20. The composition of claim 12 including a mixture of (KfC6F10CnH2nO)2PO(X) and (KfC6F10CnH2nO)PO(X)2.
 21. The composition of claim 20 wherein Kf is F, n is 1 and X is Cl.
 22. The composition of claim 20 wherein Kf is F, X is OM, M is ammonium or substituted ammonium and n is
 1. 23. The composition of claim 20 wherein Kf is F, X is OM, M is a diethanol ammonium and n is
 1. 